Schrödinger equation as part of a monument in front of Warsaw University's Centre of New Technologies

In quantum mechanics, the Schrödinger equation is a mathematical equation that describes the changes over time of a physical system in which quantum effects, such as wave–particle duality, are significant. These systems are referred to as quantum (mechanical) systems. The equation is considered a central result in the study of quantum systems, and its derivation was a significant landmark in the development of the theory of quantum mechanics. It was named after Erwin Schrödinger, who derived the equation in 1925, and published it in 1926, forming the basis for his work that resulted in him being awarded the Nobel Prize in Physics in 1933.[1][2]

In classical mechanics, Newton's second law (F = ma) is used to make a mathematical prediction as to what path a given physical system will take over time following a set of known initial conditions. Solving this equation gives the position, and the momentum of the physical system as a function of the external force F on the system. Those two parameters are sufficient to describe its state at each time instant. In quantum mechanics, the analogue of Newton's law is Schrödinger's equation for a quantum system (usually atoms, molecules, and subatomic particles whether free, bound, or localized). The equation is mathematically described as a linearpartial differential equation, which describes the time-evolution of the system's wave function (also called a "state function").[3]:1–2

The concept of a wavefunction is a fundamental postulate of quantum mechanics, that defines the state of the system at each spatial position, and time. Using these postulates, Schrödinger's equation can be derived from the fact that the time-evolution operator must be unitary, and must therefore be generated by the exponential of a self-adjoint operator, which is the quantum Hamiltonian. This derivation is explained below.

The form of the Schrödinger equation depends on the physical situation (see below for special cases). The most general form is the time-dependent Schrödinger equation (TDSE), which gives a description of a system evolving with time:[5]:143

A wave function that satisfies the nonrelativistic Schrödinger equation with V = 0. In other words, this corresponds to a particle traveling freely through empty space. The real part of the wave function is plotted here.

where i is the imaginary unit, ħ is the reduced Planck constant which is: ℏ=h2π{\displaystyle \hbar ={\frac {h}{2\pi }}}, the symbol d/dt indicates a derivative with respect to timet, Ψ (the Greek letter psi) is the state vector of the quantum system, r and t are the position vector and time respectively, and Ĥ is the Hamiltonianoperator (which characterises the total energy of the system under consideration). The position-space wave function of the quantum system is nothing but the components in the expansion of the state vector in terms of the position eigenvector |r⟩{\displaystyle \vert \mathbf {r} \rangle }. It is a scalar function, expressed as Ψ(r,t)=⟨r|Ψ⟩{\displaystyle \Psi (\mathbf {r} ,t)=\langle \mathbf {r} \vert \Psi \rangle }. Similarly, the momentum-space wave function can be defined as Ψ~(p,t)=⟨p|Ψ⟩{\displaystyle {\tilde {\Psi }}(\mathbf {p} ,t)=\langle \mathbf {p} \vert \Psi \rangle }, where |p⟩{\displaystyle \vert \mathbf {p} \rangle } is the momentum eigenvector.

Each of these three rows is a wave function which satisfies the time-dependent Schrödinger equation for a harmonic oscillator. Left: The real part (blue) and imaginary part (red) of the wave function. Right: The probability distribution of finding the particle with this wave function at a given position. The top two rows are examples of stationary states, which correspond to standing waves. The bottom row is an example of a state which is not a stationary state. The right column illustrates why stationary states are called "stationary".

The most famous example is the nonrelativistic Schrödinger equation for the wave function in the position basis Ψ(r,t){\displaystyle \Psi (\mathbf {r} ,t)} of a single particle moving in a potential V(r,t){\displaystyle V(\mathbf {r} ,t)} (for example, the electric field created by a second particle, usually much heavier, particle (but not a magnetic field; see the Pauli equation):[6])

The term "Schrödinger equation" can refer to both the general equation, or the specific nonrelativistic version. The general equation is indeed quite general, used throughout quantum mechanics, for everything from the Dirac equation to quantum field theory, by plugging in diverse expressions for the Hamiltonian. The specific nonrelativistic version is a strictly classical approximation to reality and yields accurate results in many situations, but only to a certain extent (see relativistic quantum mechanics and relativistic quantum field theory).

To apply the Schrödinger equation, the Hamiltonian operator is set up for the system, accounting for the kinetic and potential energy of the particles constituting the system, then inserted into the Schrödinger equation. The resulting partial differential equation is solved for the wave function, which contains information about the system.

The time-dependent Schrödinger equation described above predicts that wave functions can form standing waves, called stationary states (also called "orbitals", as in atomic orbitals or molecular orbitals). These states are particularly important as their individual study later simplifies the task of solving the time-dependent Schrödinger equation for any state. Stationary states can also be described by a simpler form of the Schrödinger equation, the time-independent Schrödinger equation (TISE).

where E is a constant equal to the total energy of the system. This is only used when the Hamiltonian itself is not dependent on time explicitly. However, even in this case the total wave function still has a time dependency.

In words, the equation states:

When the Hamiltonian operator acts on a certain wave function Ψ, and the result is proportional to the same wave function Ψ, then Ψ is a stationary state, and the proportionality constant, E, is the energy of the state Ψ.

In the modern understanding of quantum mechanics, Schrödinger's equation may be derived as follows.[7] If the wave-function at time t is given by Ψ(t){\displaystyle \Psi (t)}, then by the linearity of quantum mechanics the wave-function at time t' must be given by Ψ(t′)=U(t′,t)Ψ(t){\displaystyle \Psi (t')=U(t',t)\Psi (t)}, where U(t′,t){\displaystyle U(t',t)} is a linear operator. Since time-evolution must preserve the norm of the wave-function, it follows that U(t′,t){\displaystyle U(t',t)} must be a member of the unitary group of operators acting on wave-functions. We also know that when t′=t{\displaystyle t'=t}, we must have U(t,t)=1{\displaystyle U(t,t)=1}. Therefore, expanding the operator U(t′,t){\displaystyle U(t',t)} for t' close to t, we can write U(t′,t)=1−iH(t′−t){\displaystyle U(t',t)=1-iH(t'-t)} where H is a Hermitian operator. This follows from the fact that the Lie algebra corresponding to the unitary group comprises Hermitian operators. Taking the limit as the time-difference t′−t{\displaystyle t'-t} becomes very small, we obtain Schrödinger's equation.

So far, H is only an abstract Hermitian operator. However using the correspondence principle it is possible to show that, in the classical limit, the expectation value of H is indeed the classical energy. The correspondence principle does not completely fix the form of the quantum Hamiltonian due to the uncertainty principle and therefore the precise form of the quantum Hamiltonian must be fixed empirically.

The Schrödinger equation and its solutions introduced a breakthrough in thinking about physics. Schrödinger's equation was the first of its type, and solutions led to consequences that were very unusual and unexpected for the time.

The overall form of the equation is not unusual or unexpected, as it uses the principle of the conservation of energy. The terms of the nonrelativistic Schrödinger equation can be interpreted as total energy of the system, equal to the system kinetic energy plus the system potential energy. In this respect, it is just the same as in classical physics.

The Schrödinger equation predicts that if certain properties of a system are measured, the result may be quantized, meaning that only specific discrete values can occur. One example is energy quantization: the energy of an electron in an atom is always one of the quantized energy levels, a fact discovered via atomic spectroscopy. (Energy quantization is discussed below.) Another example is quantization of angular momentum. This was an assumption in the earlier Bohr model of the atom, but it is a prediction of the Schrödinger equation.

Another result of the Schrödinger equation is that not every measurement gives a quantized result in quantum mechanics. For example, position, momentum, time, and (in some situations) energy can have any value across a continuous range.[8]:165–167

In classical mechanics, a particle has, at every moment, an exact position and an exact momentum. These values change deterministically as the particle moves according to Newton's laws. Under the Copenhagen interpretation of quantum mechanics, particles do not have exactly determined properties, and when they are measured, the result is randomly drawn from a probability distribution. The Schrödinger equation predicts what the probability distributions are, but fundamentally cannot predict the exact result of each measurement.

The Heisenberg uncertainty principle is the statement of the inherent measurement uncertainty in quantum mechanics. It states that the more precisely a particle's position is known, the less precisely its momentum is known, and vice versa.

The Schrödinger equation describes the (deterministic) evolution of the wave function of a particle. However, even if the wave function is known exactly, the result of a specific measurement on the wave function is uncertain.

Quantum tunneling through a barrier. A particle coming from the left does not have enough energy to climb the barrier. However, it can sometimes "tunnel" to the other side.

In classical physics, when a ball is rolled slowly up a large hill, it will come to a stop and roll back, because it doesn't have enough energy to get over the top of the hill to the other side. However, the Schrödinger equation predicts that there is a small probability that the ball will get to the other side of the hill, even if it has too little energy to reach the top. This is called quantum tunneling. It is related to the distribution of energy: although the ball's assumed position seems to be on one side of the hill, there is a chance of finding it on the other side.

A double slit experiment showing the accumulation of electrons on a screen as time passes.

The nonrelativistic Schrödinger equation is a type of partial differential equation called a wave equation. Therefore, it is often said particles can exhibit behavior usually attributed to waves. In some modern interpretations this description is reversed – the quantum state, i.e. wave, is the only genuine physical reality, and under the appropriate conditions it can show features of particle-like behavior. However, Ballentine[9]:Chapter 4, p.99 shows that such an interpretation has problems. Ballentine points out that whilst it is arguable to associate a physical wave with a single particle, there is still only one Schrödinger wave equation for many particles. He points out:

"If a physical wave field were associated with a particle, or if a particle were identified with a wave packet, then corresponding to N interacting particles there should be N interacting waves in ordinary three-dimensional space. But according to (4.6) that is not the case; instead there is one "wave" function in an abstract 3N-dimensional configuration space. The misinterpretation of psi as a physical wave in ordinary space is possible only because the most common applications of quantum mechanics are to one-particle states, for which configuration space and ordinary space are isomorphic."

Two-slit diffraction is a famous example of the strange behaviors that waves regularly display, that are not intuitively associated with particles. The overlapping waves from the two slits cancel each other out in some locations, and reinforce each other in other locations, causing a complex pattern to emerge. Intuitively, one would not expect this pattern from firing a single particle at the slits, because the particle should pass through one slit or the other, not a complex overlap of both.

However, since the Schrödinger equation is a wave equation, a single particle fired through a double-slit does show this same pattern (figure on right). Note: The experiment must be repeated many times for the complex pattern to emerge. Although this is counterintuitive, the prediction is correct; in particular, electron diffraction and neutron diffraction are well understood and widely used in science and engineering.

The superposition property allows the particle to be in a quantum superposition of two or more quantum states at the same time. However, it is noted that a "quantum state" in quantum mechanics means the probability that a system will be, for example at a position x, not that the system will actually be at position x. It does not imply that the particle itself may be in two classical states at once. Indeed, quantum mechanics is generally unable to assign values for properties prior to measurement at all.

In Dublin in 1952 Erwin Schrödinger gave a lecture in which at one point he jocularly warned his audience that what he was about to say might "seem lunatic". It was that, when his equations seem to be describing several different histories, they are "not alternatives but all really happen simultaneously". This is the earliest known reference to the Many-worlds interpretation of quantum mechanics.[10]

The Schrödinger equation provides a way to calculate the wave function of a system and how it changes dynamically in time. However, the Schrödinger equation does not directly say what, exactly, the wave function is. Interpretations of quantum mechanics address questions such as what the relation is between the wave function, the underlying reality, and the results of experimental measurements.

where h is Planck's constant and ħ is the reduced Planck constant, h/2π. Louis de Broglie hypothesized that this is true for all particles, even particles which have mass such as electrons. He showed that, assuming that the matter waves propagate along with their particle counterparts, electrons form standing waves, meaning that only certain discrete rotational frequencies about the nucleus of an atom are allowed.[11]
These quantized orbits correspond to discrete energy levels, and de Broglie reproduced the Bohr model formula for the energy levels. The Bohr model was based on the assumed quantization of angular momentum L according to:

L=nh2π=nℏ.{\displaystyle L=n{h \over 2\pi }=n\hbar .}

According to de Broglie the electron is described by a wave and a whole number of wavelengths must fit along the circumference of the electron's orbit:

nλ=2πr.{\displaystyle n\lambda =2\pi r.\,}

This approach essentially confined the electron wave in one dimension, along a circular orbit of radius r.

In 1921, prior to de Broglie, Arthur C. Lunn at the University of Chicago had used the same argument based on the completion of the relativistic energy–momentum 4-vector to derive what we now call the de Broglie relation.[12] Unlike de Broglie, Lunn went on to formulate the differential equation now known as the Schrödinger equation, and solve for its energy eigenvalues for the hydrogen atom. Unfortunately the paper was rejected by the Physical Review, as recounted by Kamen.[13]

Following up on de Broglie's ideas, physicist Peter Debye made an offhand comment that if particles behaved as waves, they should satisfy some sort of wave equation. Inspired by Debye's remark, Schrödinger decided to find a proper 3-dimensional wave equation for the electron. He was guided by William R. Hamilton's analogy between mechanics and optics, encoded in the observation that the zero-wavelength limit of optics resembles a mechanical system—the trajectories of light rays become sharp tracks that obey Fermat's principle, an analog of the principle of least action.[14] A modern version of his reasoning is reproduced below. The equation he found is:[15]

He found the standing waves of this relativistic equation, but the relativistic corrections disagreed with Sommerfeld's formula. Discouraged, he put away his calculations and secluded himself in an isolated mountain cabin in December 1925.[18][not in citation given]

While at the cabin, Schrödinger decided that his earlier nonrelativistic calculations were novel enough to publish, and decided to leave off the problem of relativistic corrections for the future. Despite the difficulties in solving the differential equation for hydrogen (he had sought help from his friend the mathematician Hermann Weyl[19]:3) Schrödinger showed that his nonrelativistic version of the wave equation produced the correct spectral energies of hydrogen in a paper published in 1926.[19]:1[20] In the equation, Schrödinger computed the hydrogen spectral series by treating a hydrogen atom's electron as a wave Ψ(x, t), moving in a potential wellV, created by the proton. This computation accurately reproduced the energy levels of the Bohr model. In a paper, Schrödinger himself explained this equation as follows:

“

The already ... mentioned psi-function.... is now the means for predicting probability of measurement results. In it is embodied the momentarily attained sum of theoretically based future expectation, somewhat as laid down in a catalog.

This 1926 paper was enthusiastically endorsed by Einstein, who saw the matter-waves as an intuitive depiction of nature, as opposed to Heisenberg's matrix mechanics, which he considered overly formal.[22]

The Schrödinger equation details the behavior of Ψ but says nothing of its nature. Schrödinger tried to interpret it as a charge density in his fourth paper, but he was unsuccessful.[23]:219 In 1926, just a few days after Schrödinger's fourth and final paper was published, Max Born successfully interpreted Ψ as the probability amplitude, whose absolute square is equal to probability density.[23]:220 Schrödinger, though, always opposed a statistical or probabilistic approach, with its associated discontinuities—much like Einstein, who believed that quantum mechanics was a statistical approximation to an underlying deterministic theory—and never reconciled with the Copenhagen interpretation.[24]

Louis de Broglie in his later years proposed a real valued wave function connected to the complex wave function by a proportionality constant and developed the De Broglie–Bohm theory.

The Schrödinger equation is a variation on the diffusion equation where the diffusion constant is imaginary. A spike of heat will decay in amplitude and spread out; however, because the imaginary i is the generator of rotations in the complex plane, a spike in the amplitude of a matter wave will also rotate in the complex plane over time. The solutions are therefore functions which describe wave-like motions. Wave equations in physics can normally be derived from other physical laws – the wave equation for mechanical vibrations on strings and in matter can be derived from Newton's laws, where the wave function represents the displacement of matter, and electromagnetic waves from Maxwell's equations, where the wave functions are electric and magnetic fields. The basis for Schrödinger's equation, on the other hand, is the energy of the system and a separate postulate of quantum mechanics: the wave function is a description of the system.[25] The Schrödinger equation is therefore a new concept in itself; as Feynman put it:

“

Where did we get that (equation) from? Nowhere. It is not possible to derive it from anything you know. It came out of the mind of Schrödinger.

The foundation of the equation is structured to be a linear differential equation based on classical energy conservation, and consistent with the De Broglie relations. The solution is the wave function ψ, which contains all the information that can be known about the system. In the Copenhagen interpretation, the modulus of ψ is related to the probability the particles are in some spatial configuration at some instant of time. Solving the equation for ψ can be used to predict how the particles will behave under the influence of the specified potential and with each other.

The Schrödinger equation was developed principally from the De Broglie hypothesis, a wave equation that would describe particles,[27] and can be constructed as shown informally in the following sections.[28] For a more rigorous description of Schrödinger's equation, see also Resnick et al.[29]

This formalism can be extended to any fixed number of particles: the total energy of the system is then the total kinetic energies of the particles, plus the total potential energy, again the Hamiltonian. However, there can be interactions between the particles (an N-body problem), so the potential energy V can change as the spatial configuration of particles changes, and possibly with time. The potential energy, in general, is not the sum of the separate potential energies for each particle, it is a function of all the spatial positions of the particles. Explicitly:

where the A is the amplitude, k the wavevector, and ω the angular frequency, of the plane wave. In general, physical situations are not purely described by plane waves, so for generality the superposition principle is required; any wave can be made by superposition of sinusoidal plane waves. So if the equation is linear, a linear combination of plane waves is also an allowed solution. Hence a necessary and separate requirement is that the Schrödinger equation is a linear differential equation.

where d3k = dkxdkydkz is the differential volume element in k-space, and the integrals are taken over all k-space. The momentum wavefunction Φ(k) arises in the integrand since the position and momentum space wavefunctions are Fourier transforms of each other.

Likewise De Broglie's hypothesis (1924) states that any particle can be associated with a wave, and that the momentum p of the particle is inversely proportional to the wavelengthλ of such a wave (or proportional to the wavenumber, k = 2π/λ), in one dimension, by:

p=hλ=ℏk,{\displaystyle p={\frac {h}{\lambda }}=\hbar k\;,}

while in three dimensions, wavelength λ is related to the magnitude of the wavevectork:

The Planck–Einstein and de Broglie relations illuminate the deep connections between energy with time, and space with momentum, and express wave–particle duality. In practice, natural units comprising ħ = 1 are used, as the De Broglie equations reduce to identities: allowing momentum, wavenumber, energy and frequency to be used interchangeably, to prevent duplication of quantities, and reduce the number of dimensions of related quantities. For familiarity SI units are still used in this article.

Another postulate of quantum mechanics is that all observables are represented by linearHermitian operators which act on the wavefunction, and the eigenvalues of the operator are the values the observable takes. The previous derivatives are consistent with the energy operator, corresponding to the time derivative,

where p is a vector of the momentum eigenvalues. In the above, the "hats" ( ˆ ) indicate these observables are operators, not simply ordinary numbers or vectors. The energy and momentum operators are differential operators, while the potential energy function V is just a multiplicative factor.

Substituting the energy and momentum operators into the classical energy conservation equation obtains the operator:

Wave–particle duality can be assessed from these equations as follows. The kinetic energy T is related to the square of momentum p. As the particle's momentum increases, the kinetic energy increases more rapidly, but since the wavenumber |k| increases the wavelength λ decreases. In terms of ordinary scalar and vector quantities (not operators):

As the curvature increases, the amplitude of the wave alternates between positive and negative more rapidly, and also shortens the wavelength. So the inverse relation between momentum and wavelength is consistent with the energy the particle has, and so the energy of the particle has a connection to a wave, all in the same mathematical formulation.[27]

Increasing levels of wavepacket localization, meaning the particle has a more localized position.

In the limit ħ → 0, the particle's position and momentum become known exactly. This is equivalent to the classical particle.

Schrödinger required that a wave packet solution near position r with wavevector near k will move along the trajectory determined by classical mechanics for times short enough for the spread in k (and hence in velocity) not to substantially increase the spread in r. Since, for a given spread in k, the spread in velocity is proportional to Planck's constant ħ, it is sometimes said that in the limit as ħ approaches zero, the equations of classical mechanics are restored from quantum mechanics.[31] Great care is required in how that limit is taken, and in what cases.

The limiting short-wavelength is equivalent to ħ tending to zero because this is limiting case of increasing the wave packet localization to the definite position of the particle (see images right). Using the Heisenberg uncertainty principle for position and momentum, the products of uncertainty in position and momentum become zero as ħ → 0:

where σ denotes the (root mean square) measurement uncertainty in x and px (and similarly for the y and z directions) which implies the position and momentum can only be known to arbitrary precision in this limit.

One simple way to compare classical to quantum mechanics is to consider the time-evolution of the expected position and expected momentum, which can then be compared to the time-evolution of the ordinary position and momentum in classical mechanics. The quantum expectation values satisfy the Ehrenfest theorem. For a one-dimensional quantum particle moving in a potential V{\displaystyle V}, the Ehrenfest theorem says[32]

Although the first of these equations is consistent with the classical behavior, the second is not: If the pair (⟨X⟩,⟨P⟩){\displaystyle (\langle X\rangle ,\langle P\rangle )} were to satisfy Newton's second law, the right-hand side of the second equation would have to be

−V′(⟨X⟩){\displaystyle -V'\left(\left\langle X\right\rangle \right)},

which is typically not the same as −⟨V′(X)⟩{\displaystyle -\left\langle V'(X)\right\rangle }. In the case of the quantum harmonic oscillator, however, V′{\displaystyle V'} is linear and this distinction disappears, so that in this very special case, the expected position and expected momentum do exactly follow the classical trajectories.

For general systems, the best we can hope for is that the expected position and momentum will approximately follow the classical trajectories. If the wave function is highly concentrated around a point x0{\displaystyle x_{0}}, then V′(⟨X⟩){\displaystyle V'\left(\left\langle X\right\rangle \right)} and ⟨V′(X)⟩{\displaystyle \left\langle V'(X)\right\rangle } will be almost the same, since both will be approximately equal to V′(x0){\displaystyle V'(x_{0})}. In that case, the expected position and expected momentum will remain very close to the classical trajectories, at least for as long as the wave function remains highly localized in position.[33] When Planck's constant is small, it is possible to have a state that is well localized in both position and momentum. The small uncertainty in momentum ensures that the particle remains well localized in position for a long time, so that expected position and momentum continue to closely track the classical trajectories.

where ρ is the probability density, into the Schrödinger equation and then taking the limit ħ → 0 in the resulting equation, yields the Hamilton–Jacobi equation.

The implications are as follows:

The motion of a particle, described by a (short-wavelength) wave packet solution to the Schrödinger equation, is also described by the Hamilton–Jacobi equation of motion.

The Schrödinger equation includes the wavefunction, so its wave packet solution implies the position of a (quantum) particle is fuzzily spread out in wave fronts. On the contrary, the Hamilton–Jacobi equation applies to a (classical) particle of definite position and momentum, instead the position and momentum at all times (the trajectory) are deterministic and can be simultaneously known.

The quantum mechanics of particles without accounting for the effects of special relativity, for example particles propagating at speeds much less than light, is known as nonrelativistic quantum mechanics. Following are several forms of Schrödinger's equation in this context for different situations: time independence and dependence, one and three spatial dimensions, and one and N particles.

In actuality, the particles constituting the system do not have the numerical labels used in theory. The language of mathematics forces us to label the positions of particles one way or another, otherwise there would be confusion between symbols representing which variables are for which particle.[29]

where ψ(space coords) is a function of all the spatial coordinate(s) of the particle(s) constituting the system only, and τ(t) is a function of time only.

Substituting for ψ into the Schrödinger equation for the relevant number of particles in the relevant number of dimensions, solving by separation of variables implies the general solution of the time-dependent equation has the form:[15]

Since the time dependent phase factor is always the same, only the spatial part needs to be solved for in time independent problems. Additionally, the energy operator Ê = iħ∂/∂t can always be replaced by the energy eigenvalue E, thus the time independent Schrödinger equation is an eigenvalue equation for the Hamiltonian operator:[5]:143ff

H^ψ=Eψ{\displaystyle {\hat {H}}\psi =E\psi }

This is true for any number of particles in any number of dimensions (in a time independent potential). This case describes the standing wave solutions of the time-dependent equation, which are the states with definite energy (instead of a probability distribution of different energies). In physics, these standing waves are called "stationary states" or "energy eigenstates"; in chemistry they are called "atomic orbitals" or "molecular orbitals". Superpositions of energy eigenstates change their properties according to the relative phases between the energy levels.

The energy eigenvalues from this equation form a discrete spectrum of values, so mathematically energy must be quantized. More specifically, the energy eigenstates form a basis – any wavefunction may be written as a sum over the discrete energy states or an integral over continuous energy states, or more generally as an integral over a measure. This is the spectral theorem in mathematics, and in a finite state space it is just a statement of the completeness of the eigenvectors of a Hermitian matrix.

For non-interacting distinguishable particles,[34] the potential of the system only influences each particle separately, so the total potential energy is the sum of potential energies for each particle:

For non-interacting identical particles, the potential is still a sum, but wavefunction is a bit more complicated – it is a sum over the permutations of products of the separate wavefunctions to account for particle exchange. In general for interacting particles, the above decompositions are not possible.

For a constant potential, V = V0, the solution is oscillatory for E > V0 and exponential for E < V0, corresponding to energies that are allowed or disallowed in classical mechanics. Oscillatory solutions have a classically allowed energy and correspond to actual classical motions, while the exponential solutions have a disallowed energy and describe a small amount of quantum bleeding into the classically disallowed region, due to quantum tunneling. If the potential V0 grows to infinity, the motion is classically confined to a finite region. Viewed far enough away, every solution is reduced to an exponential; the condition that the exponential is decreasing restricts the energy levels to a discrete set, called the allowed energies.[30]

A harmonic oscillator in classical mechanics (A–B) and quantum mechanics (C–H). In (A–B), a ball, attached to a spring, oscillates back and forth. (C–H) are six solutions to the Schrödinger Equation for this situation. The horizontal axis is position, the vertical axis is the real part (blue) or imaginary part (red) of the wavefunction. Stationary states, or energy eigenstates, which are solutions to the time-independent Schrödinger equation, are shown in C, D, E, F, but not G or H.

The extension from one dimension to three dimensions is straightforward, all position and momentum operators are replaced by their three-dimensional expressions and the partial derivative with respect to space is replaced by the gradient operator.

where the position of particle n is rn and the gradient operators are partial derivatives with respect to the particle's position coordinates. In Cartesian coordinates, for particle n, the position vector is rn = (xn, yn, zn) while the gradient and Laplacian operator are respectively:

where e is the electron charge, r is the position of the electron relative to the nucleus (r = |r| is the magnitude of the relative position), the potential term is due to the Coulomb interaction, wherein ε0 is the electric constant (permittivity of free space) and

μ=mempme+mp{\displaystyle \mu ={\frac {m_{e}m_{p}}{m_{e}+m_{p}}}}

is the 2-body reduced mass of the hydrogen nucleus (just a proton) of mass mp and the electron of mass me. The negative sign arises in the potential term since the proton and electron are oppositely charged. The reduced mass in place of the electron mass is used since the electron and proton together orbit each other about a common centre of mass, and constitute a two-body problem to solve. The motion of the electron is of principle interest here, so the equivalent one-body problem is the motion of the electron using the reduced mass.

The wavefunction for hydrogen is a function of the electron's coordinates, and in fact can be separated into functions of each coordinate.[37] Usually this is done in spherical polar coordinates:

where R are radial functions and Ymℓ(θ, φ) are spherical harmonics of degree ℓ and order m. This is the only atom for which the Schrödinger equation has been solved for exactly. Multi-electron atoms require approximative methods. The family of solutions are:[38]

where r1 is the relative position of one electron (r1 = |r1| is its relative magnitude), r2 is the relative position of the other electron (r2 = |r2| is the magnitude), r12 = |r12| is the magnitude of the separation between them given by

In the development above, the Schrödinger equation was made to be linear for generality, though this has other implications. If two wave functions ψ1 and ψ2 are solutions, then so is any linear combination of the two:

ψ=aψ1+bψ2{\displaystyle \displaystyle \psi =a\psi _{1}+b\psi _{2}}

where a and b are any complex numbers (the sum can be extended for any number of wavefunctions). This property allows superpositions of quantum states to be solutions of the Schrödinger equation. Even more generally, it holds that a general solution to the Schrödinger equation can be found by taking a weighted sum over all single state solutions achievable. For example, consider a wave function Ψ(x, t) such that the wave function is a product of two functions: one time independent, and one time dependent. If states of definite energy found using the time independent Schrödinger equation are given by ψE(x) with amplitude An and time dependent phase factor is given by

In the 1D example with absence of a potential, V~=0{\displaystyle {\tilde {V}}=0} (or similarly V~(k)∝δ(k){\displaystyle {\tilde {V}}(k)\propto \delta (k)} in the case of a background potential constant throughout space), each stationary state of energy ℏω=q2/2m{\displaystyle \hbar \omega =q^{2}/2m} is of the form

for arbitrary complex coefficients c±{\displaystyle c_{\pm }}. Such a wave function, as expected in free space, is a superposition of plane waves moving right and left with momenta ±q{\displaystyle \pm q}; upon momentum measurement the state would collapse to one of definite momentum ±q{\displaystyle \pm q} with probability ∝|c±|2{\displaystyle \propto |c_{\pm }|^{2}}.

A version of the momentum space Schrödinger equation is often used in solid-state physics, as Bloch's theorem ensures the periodic crystal lattice potential couples f(p){\displaystyle f(p)} with f(p+K){\displaystyle f(p+K)} for only discrete reciprocal lattice vectors K{\displaystyle K}. This makes it convenient to solve the momentum space Schrödinger equation at each point in the Brillouin zone independently of the other points in the Brillouin zone.

For the time-independent equation, an additional feature of linearity follows: if two wave functions ψ1 and ψ2 are solutions to the time-independent equation with the same energy E, then so is any linear combination:

Two different solutions with the same energy are called degenerate.[30]

In an arbitrary potential, if a wave function ψ solves the time-independent equation, so does its complex conjugate, denoted ψ*. By taking linear combinations, the real and imaginary parts of ψ are each solutions. If there is no degeneracy they can only differ by a factor.

In the time-dependent equation, complex conjugate waves move in opposite directions. If Ψ(x, t) is one solution, then so is Ψ*(x, –t). The symmetry of complex conjugation is called time-reversal symmetry.

are all arbitrary constants at a given set of points, where xb, yb, zb are a set of points describing boundary b (derivatives are evaluated at the boundaries). Typically there are one or two boundaries, such as the step potential and particle in a box respectively.

As the first order derivatives are arbitrary, the wavefunction can be a continuously differentiable function of space, since at any boundary the gradient of the wavefunction can be matched.

The Schrödinger equation is consistent with probability conservation. Multiplying the Schrödinger equation on the right by the complex conjugate wavefunction, and multiplying the wavefunction to the left of the complex conjugate of the Schrödinger equation, and subtracting, gives the continuity equation for probability:[39]

If the potential is bounded from below, meaning there is a minimum value of potential energy, the eigenfunctions of the Schrödinger equation have energy which is also bounded from below. This can be seen most easily by using the variational principle, as follows. (See also below).

For any linear operator Âbounded from below, the eigenvector with the smallest eigenvalue is the vector ψ that minimizes the quantity

⟨ψ|A^|ψ⟩{\displaystyle \langle \psi |{\hat {A}}|\psi \rangle }

over all ψ which are normalized.[39] In this way, the smallest eigenvalue is expressed through the variational principle. For the Schrödinger Hamiltonian Ĥ bounded from below, the smallest eigenvalue is called the ground state energy. That energy is the minimum value of

(using integration by parts). Due to the complex modulus of ψ2 (which is positive definite), the right hand side is always greater than the lowest value of V(x). In particular, the ground state energy is positive when V(x) is everywhere positive.

For potentials which are bounded below and are not infinite over a region, there is a ground state which minimizes the integral above. This lowest energy wavefunction is real and positive definite – meaning the wavefunction can increase and decrease, but is positive for all positions. It physically cannot be negative: if it were, smoothing out the bends at the sign change (to minimize the wavefunction) rapidly reduces the gradient contribution to the integral and hence the kinetic energy, while the potential energy changes linearly and less quickly. The kinetic and potential energy are both changing at different rates, so the total energy is not constant, which can't happen (conservation). The solutions are consistent with Schrödinger equation if this wavefunction is positive definite.

The lack of sign changes also shows that the ground state is nondegenerate, since if there were two ground states with common energy E, not proportional to each other, there would be a linear combination of the two that would also be a ground state resulting in a zero solution.

The above properties (positive definiteness of energy) allow the analytic continuation of the Schrödinger equation to be identified as a stochastic process. This can be interpreted as the Huygens–Fresnel principle applied to De Broglie waves; the spreading wavefronts are diffusive probability amplitudes.[39]
For a free particle (not subject to a potential) in a random walk, substituting τ = it into the time-dependent Schrödinger equation gives:[40]

which has the same form as the diffusion equation, with diffusion coefficient ħ/2m. It is also revealed that the diffusion equation yields the Schrödinger equation in accordance with the Markov process.[41] In that case, the relation of De Broglie is reasonably derived from the correlation between diffusivities, regardless of the photon energy.[42] Thus, the relation is now not a hypothesis but an actual one expressing the nature of micro particle.

On the space L2{\displaystyle L^{2}} of square-integrable densities, the Schrödinger semigroup eitH^{\displaystyle e^{it{\hat {H}}}} is a unitary evolution, and therefore surjective. The flows satisfy the Schrödinger equation i∂tu=H^u{\displaystyle i\partial _{t}u={\widehat {H}}u}, where the derivative is taken in the distribution sense. However, since H^{\displaystyle {\widehat {H}}} for most physically reasonable Hamiltonians (e.g., the Laplace operator, possibly modified by a potential) is unbounded in L2{\displaystyle L^{2}}, this shows that the semigroup flows lack Sobolev regularity in general. Instead, solutions of the Schrödinger equation satisfy a Strichartz estimate.

was the first such equation to be obtained, even before the nonrelativistic one, and applies to massive spinless particles. The Dirac equation arose from taking the "square root" of the Klein–Gordon equation by factorizing the entire relativistic wave operator into a product of two operators – one of these is the operator for the entire Dirac equation. Entire Dirac equation:

The general form of the Schrödinger equation remains true in relativity, but the Hamiltonian is less obvious. For example, the Dirac Hamiltonian for a particle of mass m and electric charge q in an electromagnetic field (described by the electromagnetic potentialsφ and A) is:

in which the γ = (γ1, γ2, γ3) and γ0 are the Dirac gamma matrices related to the spin of the particle. The Dirac equation is true for all spin-​1⁄2 particles, and the solutions to the equation are 4-componentspinor fields with two components corresponding to the particle and the other two for the antiparticle.

For the Klein–Gordon equation, the general form of the Schrödinger equation is inconvenient to use, and in practice the Hamiltonian is not expressed in an analogous way to the Dirac Hamiltonian. The equations for relativistic quantum fields can be obtained in other ways, such as starting from a Lagrangian density and using the Euler–Lagrange equations for fields, or use the representation theory of the Lorentz group in which certain representations can be used to fix the equation for a free particle of given spin (and mass).

In general, the Hamiltonian to be substituted in the general Schrödinger equation is not just a function of the position and momentum operators (and possibly time), but also of spin matrices. Also, the solutions to a relativistic wave equation, for a massive particle of spin s, are complex-valued 2(2s + 1)-componentspinor fields.

The general equation is also valid and used in quantum field theory, both in relativistic and nonrelativistic situations. However, the solution ψ is no longer interpreted as a "wave", but should be interpreted as an operator acting on states existing in a Fock space.[citation needed]

This equation allows for the inclusion of spin in nonrelativistic quantum mechanics. Squaring the above equation yields the Schrödinger equation in 1D. The matrices η{\displaystyle \eta } obey the following properties

Here η=(γ0+iγ5)/2{\displaystyle \eta =(\gamma _{0}+i\gamma _{5})/{\sqrt {2}}} is a 4×4{\displaystyle 4\times 4}nilpotent matrix and γi{\displaystyle \gamma _{i}} are the Dirac gamma matrices (i=1,2,3{\displaystyle i=1,2,3}). The Schrödinger equation in 3D can be obtained by squaring the above equation.
In the nonrelativistic limit E−m≃E′{\displaystyle E-m\simeq E'} and E+m≃2m{\displaystyle E+m\simeq 2m}, the above equation can be derived from the Dirac equation.[44]

^Erwin Schrödinger, "The Present situation in Quantum Mechanics," p. 9 of 22. The English version was translated by John D. Trimmer. The translation first appeared first in Proceedings of the American Philosophical Society, 124, 323–38. It later appeared as Section I.11 of Part I of Quantum Theory and Measurement by J.A. Wheeler and W.H. Zurek, eds., Princeton University Press, New Jersey 1983.